Process of producing polyurethane plastics and resulting products



suitable polycarboxylic acid may be used such as, for example, succinic,oxalic, adipic, methyladipic, sebacic, glutaric, pimelic, azelaic,suberic, and the like; aromatic carboxylic acids including Vphthalic,terephthalic, isophthal- Vic, 1,2,4-benzene tricarboxylic, and the like;sulphur containing acids such as, for example, thiodiglycolic,thiodipropionic and the like; unsaturated acids such as, for example,maleic, fumarie, itaconic, citraconic, and'the like. Any suitablepolyhydric alcohol may be used such as, for example, ethylene glycol,diethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, trimethylol propane, pentaerythritol, glycerine, and the like.

Any suitable polyhydric polyalkylene ether may be used, such as, forexample the product obtained by polymerizing alkylene oxides or thecondensation product of an alkylene oxide with a small amount of acompound containing active hydrogen containing groups such as, forexample, water, ethylene glycol, propylene glycol, butylene glycol,amylene glycol, trimethylol propane, glycerine, pentaerythritol, hexanediol, hexane triol, and the like. Any suitable alkylene oxide may beused such as, for example, ethylene oxide, propylene oxide, butyleneoxide, amylene oxide, and the like. The polyhydric polyalkylene ethersmay be prepared by any known process such as, for example, the processdescribed in Wurtz in 1859 and in Encyclopedia of Chemical Technology,volume 7, pages 257 to 262 published by Interscience 'Publishers Inc.(1951) or in U.S. Patent 1,922,459.

Any suitable polyhydric polythioether may be used such as, for example,the reaction product of one of the aforementioned alkylene oxides usedin the preparation of polyhydric polyalkylene ethers With a thioetherglycol such as, for example, thiodiglycol, 3,3'dihydroxypropyl sulfide,4,4dihydroxybutyl sulfide, 1,4-(beta hydroxy ethyl) phenylenediethioether and the like.

Any suitable polyester amide may be used such as, for example, thereaction product of an amine and/ or amino alcohol with a carboxylicacid. Any suitable amine such as, for example, ethylene diamine,propylene diamine, and the like may be used. Any suitable amino alcohol,such as, for example l-hydrox Z-amino ethylene, and theglike may beused. Any suitable polycarboxylic acid may be Yused such as, forexample, those more particularly disclosed above for the preparation ofhydroxy polyesters.

Any suitable polyacetal may be used such as, for example, the reactionproduct of an aldehyde and a polyhydric alcohol. Any suitable aldehydemay be used such as, for example, formaldehyde, paraldehyde,butyraldehyde, and the like. Any of the polyhydric alcohols mentionedabove in the preparation of the hydroxyl polyesters Vmay be used.

Any suitable organic compound containing activated methylene groups maybe used such as, for example, compounds containing enolizable hydrogenatoms, such as, for example aceto acetic ester, diethyl malonate,methyl-mbutyl malonate, acetyl acetone, acetonyl acetone, and the like.

The only requirement necessary for the compounds containing activehydrogen containing groups, which groups are reactive with isocyanategroups is that the compound has a mean molecular weight of from about1000 to about 5000 and preferably from about 1500 to about 2500.

In accordance with the invention, any organic compound containing atleast two active hydrogen containing groups, which are reactive withisocyanate groups and having a molecular weight of less than about 500may be used in the rst step of the procedure in the preparation of thestorage stable intermediate. compounds included such as, for example,glycols containing urea groups such as, for example, the reactionproduct of 1 mol of urea with 2 mols of ethylene oxide, the reactionproduct of 1 mol oxazolidonc with l mol of ethanol amine, the reactionproduct of 1 mol of diethanol amine with 1 mol of `potassium cyanate,glvcols containing urethane linkages such as, for example, the reactionprod- Examples of such uct of one of the aforementioned compoundscontaining active hydrogen containing groups, which groups are reactivewith isocyanate groups with a deficiency of a polyisocyanate, glycolscontaining carbonamide groups such as, for example, the reestericationproduct of l mol of the ethanol-bis-ester of adipic acid with 2 mols ofethanol amine, glycols containing ester groups such as, for example, thereaction product of a polycarboxylic acid with an excess of a polyhydricalcohol and compounds containing tertiary nitrogen atoms such as, forexample, triethanol amine, tripropanol amine, and the like. Othercompounds suitable for use as the organic compound containing activehydrogen containing groups, which groups are reactive with isocyanategroups and which has a molecular Weight less than about 500 includeWater, simple glycols, such as, for example ethylene glycol, propyleneglycol, butylene glycol, amylene glycol, trimethylol propane, glycerine,pentaerythritol, hexane triol, and the like; glycols having aromaticring systems such as, for example, l,5-naphthalene-beta-dihydroxyethylether, hydroquinon'ebeta-dihydroxyethyl ether, and the like; diaminessuch as, for example, o-dichlorobenzidine, 2,5-dichloro-p-phenylenediamine, 3,3-dichloro-4,4diaminodiphenylmethane, hydrazine; aminoalcohols such as, for example, ethanolamine, diethanolamine,triethanolamine, and the like; amino carboxylic acids such as, forexample, beta-aminopropionic acid, piperidic acid, glycine,m-aminobenzoic acid, aminobenzoic acid, aminosuccinic acid, anthranilicacid and the like; and hydroxy carboxylic acids such as, for examplebeta-hydroxypropionic acid, alpha and beta hydroxy butyric acids,m-hydroxy benzoic acid, p-hydroxybenzoic acid, salicylic acid and thelike.

Any suitable diisocyanate may be used in the preparation of the storagestable intermediate product such as, for example, 4,4-diphenylmethanediisocyanate, the substitution products of .4,4-diphenylmethanediisocyanate such as, for example,diphenyldimethylmethane-4,4'-diisocyanate, 2,4-tolylene diisocyanate,2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylenediisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylenediisocyanate, diphenyl4,4'diisocyanate, aZo-benzene4,4'di isocyanate,diphenyl sulfone-4,4diisocyanate, dicyclohexane 4,4diisocyanate,tetramethylene diisocyanate,

hexamethylene diisocyanate and the like. It is to be understood that anysuitable diisocyanate may be used including diisocyanates containingsubstituted urea groups such as, for example, the reaction product of 2mols of V2,4-tolylene diisocyanate with 1 mol of water.

The storage stable intermediate reaction product is prepared by reactingan organic compound containing active hydrogen containing groups, whichgroups are reactive with isocyanate groups and having a molecular Weightof at least about 1000, an organic compound containing at least twoactive hydrogen containing groups, which groups are reactive withisocyanate groups and having a molecular Weight of less than about 500with a deficiency of a diisocyanate. The storage stable intermediate maybe prepared, for example, by reacting the organic compound having amolecular Weight of at least about 1000 with a quantity of adiisocyana'te less than that calculated to react with the activehydrogen groups of the compound having a molecular weight of at leastabout 1000, admixing the reaction product of the diisocyanate and theorganic compound having a molecular weight of about 1000 with theorganic compound having a molecular Weight of less than about 500 andcompleting the reaction with an additional amount of diisocyanate. Thereaction to prepare the storage stable intermediate product may also becarried out by reacting an excess of a suitable diisocyanate with theorganic compound having a molecular weight of at least about 1000 andsubsequently admixing therewith a quantity of the compound having amolecular Weight of less than about 500, which quantity is at leastsufficient to react with all of the isocyanate groups present. storagestable intermediate product can also be prepared The lare by weightunless. otherwise specified.V

by mixing the organic compound having a molecular weight of at leastabout 1000 and the organic compound having a molecular weight less thanabout 500 with a deciency of a suitable diisocyanate.

According to the invention, the storage stable intermediate prepared inaccordance with the procedure set for-th above is worked on a suitableapparatus suchas, for example, a mixing roller or a kneader while about5% to about 80% by weight of an organic compound containing activehydrogen containing groups, which groups are reactive with isocyanategroups and having a molecular weight below 500y and a quantity ofpolyisocyanate in excess of the quant-ity necessary to react with all ofthe active hydrogen containing groups present in both the storage stableintermediate and the organic compound having a molecular weight of lessthan 500 are added thereto. Theresulting composition, can then bepressed into any desired shape.

Any suitable polyisocyanate may be used in the second step of thereaction set forth in the immediately proceeding paragraph to cause thecross-linking of the storage stable intermedia-te such as, for example,4,4-diphenylmethane diisocyanate, the substitution products of 4,4'diphenylmethane diisocyanate such as,diphenyldimethylmethane-4,4-diisocyanate, 2,4-tolylene diisocyanate,2,6- tolylene diisocyanate, mixtures of 2,4 and 2,6-tolylenediisocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate,1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate,diphenyl-4,4diisocyanate, aZo-benzene-4,4 diisocyanate, diphenylsulfone-4,4-diisocyanate, dicyclohexane 4,4' diisocyanate,tetramethylene diisocyanate, hexamethylene diisocyanate, and ureadiisocyanate which is prepared by reacting 2 mols of 2,4-tolylenediisoeyanate with 1 mol of Water. Other suitable polyisocyanates includeurethdione diisocyanates which are prepared in a known manner bydimerising aromatic diisocyanates such as, for example, 2,4-tolylenediisocyanate, or l-chloro-2,4 phenylene diisocyanate; triisocyanatessuch as, for example, triphenylmethane-4,4',4-triisocyanate, thereaction,

tained. These plastic products have a high E-modulus, a v

high degree of hardness, a considerable rebound elasticity and arelatively high breaking elongation. The products of this invention findutility as construction elements in the manufacture of machines andparticularly for damping vibrations and for transmitting power. Thesematerials may also be used as substitutes for highly vulcanized naturalrubber and synthetic rubber and in some cases as substitutesfor steel. Aparticularly suitable use for the plastic compositions of this inventionis inthe handles of pneumatic drilling equipment, bearing boxes,` gearwheels, buffers, or couplings. Y

' The invention is further illustrated but'not Vlimi-ted bythegfollowing examples, inwhich parts andA percentage i-:oilvnaris 1-AProduction of a comparison vproduct About 100 partsy of an adipicacid-glycol-polyester having an OH number of about 56 are dehydrated forabout:v l hour a vacuum of about mm. at about 12.0 C. About 12.8 partsof p-phenylene diisocyanate are thenV added. After avreaction periodof'about 10' minutes at about 120 C. about 37.5 parts'of 1,4-butanediolare i therewith andthe` reaction product is heated for about minutes atabout 110"` C. 2

ef A storage stable intermediate results having properties similar tocrude rubber and has a Defo hardness of about 1900. The storage stableintermediate can be cross-linked by known procedures to form anelastomeric product by incorporating therein on a rolling mill about 6parts of dimeric tolylene diisccyanate to each parts of the storagestable intermediate, with subsequent pressing at about In accordancewith this invention the storage stableV intermediate prepared by theprocedure set forth in Example l-A has incorporated therein on a rollingmill about 10 parts of p-phenylene-beta-dihydroxyethyl ether and about1S parts by weight of dimeric tolylene diisocyanate for each 100 partsof the storage stable intermediate. The product is .then pressed for atleast about 30 minutes at about 130 C. The resulting product has thefollowing properties: i

Thickness ofthe test sheet 6 mm. Tensile strength 237 kg./cm.2. Breakingelongation 510%. Permanent elongation 19 Shore A hardness 92. Reboundelasticity 42%. K Loading at 20% elongation 73kg./cm.2. Loading at 300%elongation lig/cm?.

EXAMPLE 'r-C In accordance with this invention the storage stableintermediate prepared by the procedure set forth in Example l-A hasincorporated therein on a rolling mill about 20 parts ofp-phenylene-beta-dihydroxyethyl ether and about V30 parts by weight ofdimeric tolylene diisocyanate for each 100 parts of the storage stableintermediate. The product 4is then pressed for at least about 30 minutesat about 130 (l.V The resulting product has the following properties:

Thickness of the test sheet 6.1 mm. Tensile strength' 249 kg./crn.2YBreaking elongation 345%. Permanent elongation 21%.

Shore A hardness 96. Rebound elasticity 39%. Loading at 20% elongation172 kg./cm.2.

. Loading at300% elongation 181 lig/cm?.

EXAMPLE 1-D In accordance with this invention the storage stableintermediate Vprepared by the procedure set forth iii-EX- ample 1A hasincorporated therein on a rolling mill about 30 parts ofkp-phenylene-beta-dihydroxyethyl ether and about 42 partsy by weight ofdimeric tolylene diisoi cyanate for each 100 partsofthe storage stableintermediate. The product is thenpressed for atA leastabout 30 minutesat about 130? C. The resulting product has the following properties:

Notch-impact toughness (Dynstat)` e 100%,unbrokeng Maximum stress atcommencement Y 1f .Y offlow' 230kg./crn.2.

7 Brinell hardness after 10 seconds 348. Brinell hardness after 60seconds 343. Maximum swelling in methylene chloride 90% EXAMPLE 2-AProduction of a comparison product To about 100 parts of a polythioetherprepared by reacting 2 mols of thiodiglycol with 1 mol of triethyleneglycol and having an hydroxyl number of about 67.5 and an acid number ofabout 0.3 is admixed about 0.9 part of water. About 12.5 parts oftolylene diisocyanate are then added and the reaction mass is heated forabout hours at about 90 C. The rubber-like storage stable intermediatereaction product formed, which has a Defo hardness of about 900 is thenadmixed on a roller mill with about 10 parts of4,4diisocyanato3,3dimethyl diphenyl urea to each 100 parts of theintermediate. A test sheet pressed at least for about 30 minutes atabout 130 C. has the following mechanical properties:

Thickness of the test sheet 6 mm. Tensile strength 150 lig/cm?. Breakingelongation 390%. Permanent elongation 3 Shore A hardness 69 Reboundelasticity 58 Loading at elongation 16 kg./cm.2. Loading at 300%elongation 56 lig/cm?. Maximum swelling in methylene chloride 320%.

EXAMPLE Z-B In accordance with this invention the polythioether storagestable intermediate prepared in Example 2-A has incorporated therein ona roller mill about 11.5 parts of p-phenylene dihydroxycthyl ether andabout 45 parts of 4,4diisocyanate3,3'-dimethyldiphenyl urea to abouteach 100 parts of the storage stable intermediate. The inal product ispressed for at least about minutes at about 130 C. The resulting productis a rigid plastic having the following properties:

Thickness of the test sheet 2 mm. Tensile strength 310 kg./cm.'-. Limitbending stress 205 kg./cm.2. Impact toughness 100% unbroken. Notchimpact toughness 100%, unbroken. Maximum stress at commencement of flow195 kg./cm.2. Brinell hardness: Y

(a) After 10 seconds 246. (IJ) After 60 seconds 241. Maximum swelling inmethylene chloride 36% EXAMPLE 3-A Production of a comparison product Toabout 100 parts of an adipic-diethylene-glycol polyester having anhydroxyl number of about 60 and an acid number of about 1 are admixedabout 0.9 part of water and about 4.4 parts of 1,4-butene diol.Thereafter about 19.8 parts of tolylene diisocyanate are added and thereaction product is heated for about 15 hours at about 90 C. Theresulting crude rubber-like storage stable intermediate reactionproduct, which has a Defo hardness of about 1200 is admixed on a rollermill with about 8 parts of 4,4diphenylmethane-diisocyanate for abouteach 100 parts of the storage stable intermediate. The resulting productis pressed for at least about 30 minutes at about 125 C. The materialhas the following properties:

Thickness of the test sheet 5.9 mm. Tearing strength 220 kg./crn.2.Breaking elongation 790%. Permanent elongation 11% Shore A hardness 62 8Rebound elasticity 41% Loading at 20% elongation 4 kg./cm.2. Loading at300% elongation 29 kg./cm.2. Maximum swelling in methylene chloride 460%EXAMPLE 3-B In accordance with this invention, the storage stable cruderubber-like intermediate has incorporated therein on a roller mill about14.5 parts of o,o'-dichlorobenzidine and about 30 parts of4,4diphenylmethane-diisocyanate for each parts of the storage stableintermediate. The product obtained is pressed at about 130 for about 60minutes. The material has the following properties:

Thickness of the test plate 2 mm. Tensile strength 280 kg./ cm?. Limitbending stress 233 kg./cm.2. Impact toughness 100%, unbroken. Notchimpact toughness 94% unbroken. Maximum stress at commencement of ilow214 lig/cm?. Brinell hardness:

(a) After 10 seconds 279. (b) After 60 seconds 274. Maximum swelling inmethylene chloride 96%.

I EXAMPLE 4-A Production of a com parz'son product To about 100 parts ofan adipic acid-glycol-polyester having an hydroxyl number of about 56and an acid nurnber of about 0.8, which has been previously dehydratedat about C. and 50 mm. for about 1 hour, are added with stirring about10.8 parts of tolylene diisocyanate. After a reaction period of about 10minutes at about 120 C., about 5.6 parts of o,odichlorobenzidine areadrnixed therewith and the reaction product is heated for about 5 hoursat about 110 C. The crude rubber-like storage stable intermediatereaction product having a Defo hardness of about 230() is admixed on aroller mill with about 8 parts of dimeric tolylene diisocyanate for each100 parts of the storage stable intermediate. A test sheet pressed forabout 20 minutes at about 110 C. has the following properties:

Thickness of the test sheet 6 mm. Tearing strength 389 kg./cm.2.Breaking elongation 754% Permanent elongation 14% Shore A hardness 79Rebound elasticity 48%.

Load at 20% elongation 21 kg./cm.2. Load at 300% elongation 81 kg./cm.2.

Maximum swelling in methylene chloride 364% In accordance with thisinvention about 28 parts of 1,5- naphthalene dihydroxyethyl ether andabout 35 parts of dimeric tolylene diisocyanate for each 100 parts ofthe storage stable `intermediate are incorporated into the storagestable intermediate crude rubber-like reaction product of Example 4A ona roller mill. A rigid .plastic material is obtained having thefollowing physical properties:

Thickness of the test sheet 2 mm. Tensile strength 418 kg./cm.2. Limitbending stress 402 kg./cm.2. Maximum stress at commencement of ow 396kg./cm.2.

Brinell hardness:

(a) After 10 seconds 496.

(b) After 60 seconds 492.

Maximum swelling in methylene chloride 76% 9 I EXAMPLE S-A Production ofa comparison product To about 100 parts by weight of a polyalkyleneether prepared by polymerizing tetrahydrofuran and .having an hydroxylnumber of about 46 are admixed about 0.9 part of water and 0.7 part ofbutenediol. Thereafter about 1l Y parts of tolylene diisocyanate areadded and the reaction mass is heated for about 15 hours at about 90 C.to obtain a rubber-like storage stable intermediate hav-ingV a Defohardness; of about2000. About 8 parts of p-phenylene diisocyanate areadmixed therewith on .a-'roller mill .for each 100 parts of the storagestable-intermediate. A

test sheet pressed for about 30 minutesat about 130 C.

has the following mechanical properties: l l

Thicknesso-f the test sheet 6 mm. v Tearing strength 220 kg/c'm?.Breaking elongation 460%. o Permanent elongation Shore A hardness 60Rebound elasticity 62%. Load at 20% elongation v18 kg./cm.2. Load at300% elongation 62 kg] cn1.2.-` Maximum swelling in methylene chloride460% EXAMPLE 543 i is' EXAMPLE 6`B n o In accordance with this inventionabout 10 parts of 1,4-butanediol and about 35 .parts of dimer-ictolylene diisocyanate per A100 parts of .thestorage stable intermediateof Example 6"-A `are incorporated into the storage stable intermediate on a roller mill. A test sheet pressed forfabout minutes at about 130Cfhas the follow# `ing properties:

y Thickness of the test sheet 2 i ensile strength 290 lig/cm?. Limitbending stress V. 185 lig/cm?. Impact toughness 100%, unbroken. Notchimpact toughness' 100%, unbroken. Maximum stress at commencement of iiow190 lig/cm?. Brinell hardness: i 'l l' (a) After 10 seconds 238. (b)After 60 seconds 233. Maximum swelling in methylene chloride 95%.

" EXAMPLE 6-C In accordance'iwith this inventionabout 1.1.5 parts of lp-phenylene dihydroxyethyl ether and labout 2'5 parts of p-phenylenediisocyanatel for each 100 parts of the storage stable intermediate areincorporated into'the storageL stable intermediate'of Example `5-,A on aroller mill. A test sheet pressedfor about 30 minutes at about 130 C.results in a rigid-plastic having the following properties;r y YProductionfof a comparison product To about100` partsof an :adipicacidglycol-polyester having an OH numberof about 56 which Ahasprev1ously Thickness of the test sheet j 6 mm;

Tensile strength V340 lig/cin?. Limit stress 315 lig/cmg?. impacttoughness 100%, unbroken. o Notch impactv toughness 96%, unbroken.. oMaximum stress at commencement of Y i c flow 310kg./'cm.2; Brinellhardness: f

l.-(cz) After l0 seconds 364.

(b.) After 60 seconds 361.

In Vaccordancewith this invention the storage stable intermediate ofExample 6-A hasl .incorporated therein on a roller mill about 30 partsof 3,3-dichloro-4,4diami nodiphenylmethane and about parts of dimerictolylene diisocyanate per 100 parts of the storage stable intermediate.-A test sheet pressed for about 30 minutes at Vabout 130 C. has thefollowing properties:

.. Maximum swelling in methylene chlobeen dehydrated for aboutl hourfatabout 120 C. .and

about mm. are added about V20 parts of 4,4"diphenyl" methanediisocyanate After fa reactiontime ofV about 10 minutes at about 120 C.,about 7.7 parts of p-phen- `ylene dihydroxyethyl ether yare added andthereactionproduct is-heated forabout'l'S hours at about r110"C. A crude.rubbenlike storage stable intermediate product is formed having aDefohardn'ess ofy 2200. This product `is subsequently reacted with about6 parts of dimeric toiylene-diisocyanate foreach 100'. parts of thestorageV ing properties:

I VVstable intermediate on la roller mill. A test sheet pressed atabout'13 0 C. for a'ooutfa'Ol minutes has-the follow- Thickness 'of thetest sheet 6 mm'.` TearingV strength 270 lig/cm?. Breaking elongation5620%.

Permanent'elongation 18%. d `Shore A hardness 82. Rebound elasticity45%. y Load at. 20% elongation 1 21 kg/cm2: Load atf 300% 'elongation f74 kg./cm.2. Maximum' swelling in methylene-chlo--.

ride j. 85%.

In some cases theproducts produced according to the present process areof such a high hardness that `it was 4 5 impossible to subject theproducts to. the same tests as the. comparison product. It was necessaryto run Vdifierent tests for the hardV products.

Although the invention has been described in cori-V Asiderable detail inthe foregoing, in order -toproperly illustrate theinvention, it is tobeundrstood that vthe purpose of such detail is solely to illustratertheembodiments of the `invention and that modicationscan be made by thoseskilled in the art Without departing from thejspirit and scope of theinvention as set forth in the i V* n Y claims. g v

Whatl is claimed is t. 'i

l'. The processv of producing polyurethane plastics i which comprises.preparing a storage stable intermediate in a first step by reacting afirst organic compound containingactive hydrogen containing groups yinthe v `molecule, said groups being reactive with isocyanate groups, saidiirst compound havingamolecular weight of atleast about 100,0,"a` secondorganic compound containing active hydrogen containing'groups in themolecule,

said Vgroups being reactive kwithis'ocyanarte groups, ,said

second compound having "a molecular weight of less than 'about 500 witha` deficiency of an organic'diisocyanate .and curing said storage stableintermediate in a second step by adrnixing therewith anorganic compoundcontaining active hydrogen containing groups in"V4 the molecule,

saidY groups` being reactive"withisocyarmte groups, -said compoundhaving Va molecularIweight.offlessthan about .500,iand anorganic'polyisocyanate in excess of` the amount necessary to react withall theactive hydrogen containing groupsofY the storage stableintermediate and' the organic compound containing active hydrogen con-'taining groups added in said second step.

2. The process of claim 1 wherein the organic compound containing activehydrogen containing groups in the molecule, and having a molecularweight less than about 500 is an organic compound containingaliphatically-bound active hydrogen containing groups selected from thegroup consisting of amino and hydroxyl groups.

3. The process of producing polyurethane plastics which comprisespreparing a storage stable intermediate in a first step by reacting arst organic compound containing active hydrogen containing groups in themolecule,

said groups being reactive with isocyanate groups, said 'first compoundhaving a molecular weight of at least about 1000, having an hydroxylnumber of from about to about 150, a second organic compound containingactive hydrogen containing groups in the molecule, said groups beingreactive with isocyanate groups, said second compound having a molecularweight less than about 500 with a deficiency of an organic diisocyanate,admixing with said storage stable intermediate an organic compoundcontaining active hydrogen containing groups in the molecule, saidgroups being reactive with isocyanate groups, said compound having amolecular weight less than about 500 and an excess of an organicpolyisocyanate, said excess being at least sufiicient to react with allthe active hydrogen containing groups present in the storage stableinterweight less than 500.

4. In the process for preparing polyurethane plastics from a storagestable intermediate prepared by reacting a first organic compoundcontaining active hydrogen containing groupsin the molecule, said groupsbeing reactive with isocyanate groups, said first compound having amolecular weight of at least about 1000, a second organic compoundcontaining active hydrogen containing groups in the molecule, saidgroups being reactive with isocyanate groups, said second compoundhaving a molecular weight of less than about 500 With a deficiency of anorganic diisocyanate the improvement which comprises curing saidintermediate by admixing therewith an organic compound containing activehydrogen containing groups in the molecule, said groups being reactivewith isocyanate groups, said compound having a molecular weight of lessVthan about 500 and a quantity of an organic polyisocyanate at leastsufficient to react with the active hydrogen containing groups of saidstorage stable intermediate and said organic compound having a molecularweight less vthan about 500.

5. A polyurethane plastic product prepared by the process whichcomprises preparing a storage stable intermediate in a first step byreacting a first organic compound containing active hydrogen containinggroups in the molecule, said groups being reactive with isocyanategroups, said first compound having a molecular weight of at least about1000, a second organic compound containing active hydrogen containinggroups in the molecule, said groups being reactive with isocyanategroups, said second compound having a molecular weight of less thanabout 500 with a deficiency of an organic diisocyanate and curing saidstorage stable intermediate in a second step'by admixing therewith anorganic compound containing active `hydrogen containing groups in themolecule, said groups first compound having molecular Weight of atleastabout 1000, a second organic compound containing active hydrogencontaining groups in the molecule, said groups Aall the active hydrogencontaining groups of the storage stable intermediate and the organiccompound containing active hydrogen containing groups added in saidsecond zstep, V

7. The process of producing polyurethane plastics which comprisespreparing a storage stable intermediate in a first step by reacting afirst organic compound containing active hydrogen containing groups inthe molecule, said groups being reactive with isocyanate groups, saidfirst compound having a molecular weight of at least about 1000 andselected from the group consisting of hydroxyl polyesters prepared bythe process which comprises reacting a polycarboxylic acid with apolyhydric alcohol, polyhydric polyalkylene cthers, polyhydricpolythioethers, polyesteramides, polyacetals and organic compoundscontaining activated methylene groups, a second organic compoundcontaining active hydrogen containing groups in vthe molecule, saidgroups being reactive with isocyanate groups, said second compoundhaving a molecular weight of less than about 500 and selected from thegroup consisting of diamnes, polyhydric alcohols, amino alcohols, aminocarboxylic acids and hydroxy carboxylic acids with a deficiency of anorganic diisocyanate and curing said storage,v stable intermediate in asecond step by admixing therewith an organic compound'containing activehydrogen containing groups in the molecule, said groups being reactivewith isocyanate groups, said compound having a molecular weight of lessthan about 500 and selected from the group consisting of diamines,polyhydric alcohols, amino alcohols, amino carboxylic acids and hydroxycarboxylic acids and an organic polyisocyanate in excess of the amountnecessary to react with all the active hydrogen containing groups of thestorage stable intermediate and the organic compound containing activehydrogen containing groups added in said second step.

8. The process of producing polyurethane plastics which comprisespreparing a storage stable intermediate in a first step by reacting afirst organic compound containing active hydrogen containing groups inthe molecule, said groups being reactive with isocyanate groups, saidfirst compound having a molecular weight of at least about 1000 and anhydroxyl number of from about 30 to about V and selected from the groupconsisting of hydroxyl polyesters prepared by the process whichcomprises reacting a polycarboxylic acid with a polyhydric alcohol,polyhydric polyalkylene ethers, polyhydric polythioethers,polyesteramides, polyacetals and organic compounds containing activatedmethylene groups, a second organic compound containing active hydrogencontaining groups in the molecule, said groups being reactive withisocyanate groups, said second compound having a molecular weight Yorganic 'compounds 'i3 organicpolyisocyanate, said excess being at leastsuliicien to reactwith all the active hydrogen containing groups presentin the Storage stable intermediate and the organic compound having amolecular Weight less than 500.

i 9L Inthe process for preparing polyurethane plastics from va storagestable intermediate prepared by reacting a first organic compoundcontaining .active hydrogen containing groups in the molecule, said'groups being reactive with isocyanate groups, said 1iirst compoundhaving a molecular weight of at least about 1000 and selected from thevgroup consisting of hydroxyl polyesters prepared by the process whichcomprises reacting a polycarboxylic acid with a polyhydric alcohol,polyhydric polyalkylene ethers, polyhydric polythioethers,polyesteramideafpolyacetals and organic compounds -containing activatedmethylene groups, a second organic compound containing active hydrogencontaining groups in the molecule, said groups being reactive withisocyanate groups, said second compound having a molecular weight ofless than about 500 and selected from the group consisting of diamines,polyhydric alcohols,amino alcohols, amino carg boXylic acids -andhydroxy carboxylic acids with a deficiency of an organic diisocyanate,the improvement therewith an organic compound containing active hydrogencontaining groups in the molecule, said groups being reactive withisocyanate groups, said compound having Y ,a molecular weight of lessthanrabout 500 and selected from the group consisting of diamines,polyhydric alcohols, amino alcohols, amino carboxylic acids and hydroxycarboxylic acids and a quantity ofan organic polyisocyanate at leastsufficient to react with Ythe active hydrogen containing groups of saidstorage stableintermediate and said organic compound having a molecularweight less than about 500. l Y Y v10. A polyurethane plastic productprepared by the process which comprises preparing a storage stableintermediate in a iirst step by reacting a first `organic compoundycontaining active hydrogen containing groups in the molecule, saidgroups being reactive with isocyanate groups, said first compound havinga molecular weight of at least about 1000 and selected from the groupcon- 1 sisting of hydroxyl polyesters prepared bythe process whichcomprises reacting a polycarboxylicV acid with a polyhydric alcohol,polyhydric polyalkylene ethers, polyhydric polythioethers,polyesteramides, polyacetals and containing activated methylene groups,a second organic compound containing active hydrogen' containinggroupsin the molecule, saidgroups being reactive with isocyanate groups,saidfsecond compound having a molecular Weight of less than about 500and selected from the group consistingof diamines, polyhydric alcohols,amino-alcohols, aminor carboxylic acids and hydroxy carboxylic acids,with a deficiency of an organic diisocyanate and curing said storagestable intern mediate in a second step by admixingv therewith an organiccompound containing active hydrogen containing groups prises reacting apolycarboxylic acid with a polyhydric alcohol, polyhydric polyalkyleneethers, polyhydric polytboethers, polyesteramides, polyacetals andorganic compounds containing activated methylene groups,-a secondorganic compound containing active hydrogen containing groups in themolecule, said groups being reactive with isocyanate groups, said secondcompoundV having a molecular weight of less thanabout 500 and selected'from the group consisting of diamines, `polyhydric alcohols, aminoalcohols, amino carboxylic acids and hydroxy carboxylic acids with adeficiency of an organic diiso* cyanate and curing said storage stableintermediate in a second step by admixing therewith from about 5% toabout 80% by weight of an organic compound containing active hydrogencontaining groupstin the molecule, said groups being reactive withisocyanate groups, said compound having a molecular weight of less thanabout 500 and selected from the group consisting of diamines, polyhydricalcohols, amino alcohols, amino carboxylic acids and hydroxy carboxylicacids and an organic poly- Viirst compound having armolecular vweight ofYatleast about 1000 and selected from the group consisting Vof hydroxylpolyesters prepared by'the process which con- Aprises reacting apolycarboxylicacid withfa polyhydric alcohol, polyhydric polyalkyleneethers, polyhydric polythioethers, polyesteramides, polyacetals andorganic compounds containing activated methylene groups, a secondorganic compound containing active hydrogen containing groups in 'themolecule, said groups being reactive with Visocyanate vgroupsV saidsecond compound having a molecular Weight of less than about 500 andselected from the groupk consisting of `diamines,: polyhydric alcohols,

Y amino alcohols, amino carboxylic yacidsandv hydroxy carboxylic acidswith a deficiency of an organic diisocyanate and curing said storagestable intermediate in a second step by admixing therewith from about10% yto about v 'i 50%v by'weight of an organic compound containinglactive hydrogen containing groups in the molecule, `said groups beingreactive withv isocyanate groups, saidV compound having a molecularweight of less than about 500 and f selected from the group consistingof diamines, poly- .'hydric alcohols, amino alcohols, amino carboxylicacids in the molecule, said groups being reactive with isocyanate igroups, said compound having a molecular weight'of less than about50v0andselected from' the group consisting of diamines, polyhydricfalcohols,aniinoalcohols, amino carboxylic acids and-hydroxy carboxylic acids and,anorganic polyisocyanateV in excess of the amountnecessary to reactwith all the active Vhydrogen containing groups 'of ,the storage stableintermediate and the organidcom- 'pound containing activefhydrogencontaining groups Y added in said second step. A Y 11. The processof'producing polyurethane `plastics tainingactive hydrogen containinggroups in the molecule,v

said groups being 4reactive with isocyallate',group's,l said Y firstcompound having Vamolecular weigh't'fofi,"atleast and hydroxy carboxylicacids and an organic polyisoc'yanate in excessof the amountv necessaryto react with all the active hydrogen containing groups ofthe storagestable intermediate and `the organic compound containing activelhydrogen containing groups added in said secondV step. L t

' `hydroxyl .polyester prepared by reacting a polycar'ofcxylic acid'withfa polyhydric alcohol. f

having a molecular weight of atleast about V1000 is a I polyhydricpolyalkylene other.'

about 1000 and selected fromrthe group consisting of hyl* :"*droxyl'polyesters `prepared by -th`e process whichfpcoml15. Ihefprocess ofclaimi wherein therorgan'iccompound having a molecular weight'less than500 isa glycol. .16. The `process of claiingv wherein the organicVcompound havingV afrrrolecular'y weight lessvk thanV 500v is an `organicdiamine. Y i, 1.7,V The processvv o fnclaim wherein the organic poly-,g

isocyanate ,isan aromatic diisocyanate.'k i

y 13. The process of claim v 6 wherein the organic corn- 'u poundcontaining active hydrogen containing groups and 1 having a molecularWeight ofat least about 1000 is a 15 18. The process of claim 17 whereinthe aromatic diisocyanate is 4,4dipher1y1methane diisocyanate.

19. The process of claim 17 wherein the aromatic diisocyanate istolylene diisocyanate.

20. The process of claim 17 wherein the aromatic diisocyanate is dimerictolylene diisocyanate.

References Cited in the le of this patent UNITED STATES PATENTS SeegerJan. 13, 1953 15 A Seeger Sept. 2, Shrimpton et al Ian. 20, SchollengerJan. 27, Walter I an. 27, Muller Apr. 21, Fauser May 26, Best et alSept. 22, Nischk et al. Nov. 10, Muller et a1 Aug. 29, Scott et a1 Sept.26, Muller et a1 Dec. 26,

1. THE PROCESS OF PRODUCING POLYURETHANE PLASTICS WHICH COMPRISESPREPARING A STORAGE STABLE INTERMEDIATE IN A FIRST STEP BY REACTING AFIRST ORGANIC COMPOUND CONTAINING ACTIVE HYDROGEN CONTAINING GROUPS INTHE MOLECULE, SAID GROUPS BEING REACTIBE WITH ISOCYANATE GROUPS, SAIDFIRST COMPOUND HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 1000, ASECOND ORGANIC COMPOUND CONTAINING ACTIVE HYDROGEN CONTAINING GROUPS INTHE MOLECULE, SAID GROUPS BEING REACTIVE WITH ISOCYANATE GROUPS, SAIDSECOND COMPOUND HAVING A MOLECULAR WEIGHT OF LESS THAN ABOUT 500 WITH ADEFICIENCY OF AN ORGANIC DIISOCYANATE AND CURING SAID STORAGE STABLEINTERMEDIATE IN A SECOND STEP BY ADMIXING THEREWITH AN ORGANIC COMPOUNDCONTAINING ACTIVE HYDROGEN CONTAINING GROUPS IN THE MOLECULE, SAIDGROUPS BEING REACTIVE WITH ISOCYANATE GROUPS, SAID COMPOUND HAVING AMOLECULAR WEIGHT OF LESS THAN ABOUT 500, AND AN ORGANIC POLYISOCYANATEIN EXCESS OF THE AMOUNT NECESSARY TO REACT WITH ALL THE ACTIVE HYDROGENCONTAINING GROUPS OF THE STORAGE STABLE INTERMEDIATE AND THE ORGANICCOMPOUND CONTAINING ACTIVE HYDROGEN CONTAINING GROUPS ADDED IN SAIDSECOND STEP.
 5. A POLYURETHANE PLASTIC PRODUCT PREPARED BY THE PROCESSWHICH COMPRISES PREPARING A STORAGE STABLE INTERMEDIATE IN A FIRST STEPBY REACTING A FIRST ORGANIC COMPOUND CONTAINING ACTIVE HYDROGENCOANTAINING GROUPS IN THE MOLECULE, SAID GROUPS BEING REACTIVE WITHISOCYANATE GROUPS, SAID FIRST COMPOUND HAVING A MOLECULAR WEIGHT OF ATLEAST ABOUT 1000, A SECOND ORGANIC COMPOUND CONTAINING ACTIVE HYDROGENCONTAINING GROUPS IN THE MOLECULE, SAID GROUPS BEING REACTIVE WITHISOCYANATE GROUPS, SAID SECOND COMPOUND HAVING A MOLECULAR WEIGHT OFLESS THAN ABOUT 500 WITH A DEFICIENCY OF AN ORGANIC DIISOCYANATE ANDCURING SAID STORAGE STABLE INTERMEDIATE IN A SECOND STEP BY ADMIXINGTHEREWITH AN ORGANIC COMPOUND CONTAINING ACTIVE HYDROGEN CONTAININGGROUPS IN THE MOLECULE, SAID GROUPS BEING REACTIVE WITH ISOCYANATEGROUPS, SAID COMPOUND HAVING A MOLECULAR WEIGHT OF LESS THAN ABOUT 500,AND AN ORGANIC POLYISOCYANATE IN EXCESS OF THE AMOUNT NECESSARY TO REACTWITH ALL THE ACTIVE HYDROGEN CONTAINING GROUPS OF THE STORAGE STABLEINTERMEDIATE AND THE ORGANIC COMPOUND CONTAINING ACTIVE HYDROGENCONTAINING GROUPS ADDED IN SAID SECOND STEP.